DE3206379C2 - - Google Patents

Description

The invention relates to free-flowing, spray-dried hollow spheres. those for the production of particulate, Builders and synthetic nonionic organic surfactant containing detergent composition are suitable, as well as their Use for the production of free-flowing, spray-dried Detergent compositions.

In recent years, water softening has become insoluble Aluminosilicates such as hydrated zeolites as builders used in detergent compositions. First there was interest in zeolites due to the need to produce phosphate-free detergent compositions.  

Trisodium nitrilotriacetate and other salts of nitrilotriacetic acid, which as a potential replacement for the phosphates had been proposed, especially for pentasodium tripolyphosphate, that contains to a large extent in builders Detergent compositions had been used were feared by some bodies and accordingly were in the United States of America products containing nitrilotriacetate for years the market. However, there was never any serious doubt that phosphates are safe for humans, and recently was the unfavorable assessment of the use of nitrilotriacetates in detergent compositions by the authorities withdrawn from the United States. Although therefore certain phosphate-free detergents continue to be manufactured for areas that lie on lakes and rivers, where phosphate is a necessary nutrient for algae growth, and thereby can lead to some eutrophication of the water, are detergents containing phosphate and / or nitrilotriacetate back on the market.

Although zeolites, preferably zeolite A and in particular hydrated zeolite 4A already as builders in phosphate-free and detergents free of nitrilotriacetates they have now become useful components of improved detergents and the underlying ones  Hollow beads proved to be the phosphate (s) and / or Nitrilotriacetate included. Usually about 6 to 12% water-soluble sodium silicate in Crutch mixtures used, from which spray-dried hollow spheres or Detergent compositions are made. The silicate was used because of its effect, the other components to bind the hollow spheres so that stable hollow spheres be obtained, and it has been found to be educational contributes to a networked internal structure of the hollow spheres. It also has an anti-corrosive effect and prevents a chemical Attack on the aluminum parts of the washing machine and other devices with which the detergent solution is in contact can come. However, it has been found that in the earlier used proportions of z. B. 8 to 10% of the finished product the combination of water-soluble silicate and zeolite in the crutch mixture to form aggregates of these Materials in the spray-dried hollow spheres that leads undesirably on the washed materials deposit and affect the color of the laundry. According to the invention are with certain amounts of zeolite, bentonite and water soluble builder with little or no water soluble Silicate spray-dried hollow spheres with sufficient mechanical strength for commercial use receive, which at the same time less zeolite or zeolite Store silicate aggregates. Even if a small amount If there is silicate, the bentonite appears to be the tendency of the  Zeolite and silicate, larger particles than they normally are present in the zeolite to form, to counteract. This eliminates the unwanted deposition of zeolite or Prevents zeolite silicate particles on the washed fabrics or reduced. In addition, those containing bentonite disintegrate Compositions much easier in wash water and are distributed in it, probably in turn due to the Presence of bentonite. Another advantage of the invention Compositions containing little or no silicate, is that the carbonate and / or bicarbonate formulations containing the presence of the gelation preventive materials require an excessive To prevent thickening of the crutch mixture. These Additives are usually not necessary if the main builder the detergent consists of a phosphate and if little or no carbonate and / or bicarbonate is present. For phosphate-free formulations, the amounts are often noticeable contain carbonate and / or bicarbonate, the omission of gel-preventing materials decisive advantage, both in terms of processing as well as in terms of economy.

From the prior art for the production of detergents, Water softening compositions and softening detergents it is known that various detergent compositions  with one or more zeolites, bentonite, silicate, Phosphate, nitrilotriacetate, quaternary ammonium compounds (Fabric softener) and other components can be, usually using synthetic organic detergent ingredients. In extensive lineups, sometimes referred to as "detergent lists" almost all materials are listed that are for any Purposes in detergent and softening compositions used, but they do not contain the clear teaching or reference to the formulations according to the invention, especially not on phrases that have little or contain no soluble silicate. The meaning of Bentonite, the "lubricating" water between his tile is obviously not recognized not even the combination of binding and explosive properties of the "hydrated" bentonite. Many known formulations also contain significant amounts Sodium sulfate, a filler that may be the improved physical properties of the product particles, but not required in the compositions according to the invention which therefore has a higher content of active ingredients, including builders.  

A detergent composition was known from US Pat. No. 4,166,039, where the nonionic surfactant is already in the crutcher mixture is present, the task to be solved was a To produce Crutcher mixture that is homogeneous because it is non-ionic Surfactant due to its oily nature tends to be in the crutcher mixture to be available as a separate phase. For this, a Detergent composition of kaolinite or bentonite, one nonionic surfactant, and a builder suggested where if the builder is a phosphate, bentonite, and if the builder is not a phosphate, kaolinite is used. The The disadvantage here is that nonionic surfactant is used for spray drying evaporates and escapes from the spray drying tower, causing surfactant is lost and the environment is polluted.

A method for was also known from GB-PS 20 63 289 Manufacture free-flowing powder detergent from one aqueous slurry containing anionic surfactant, a Builder, which consists partly of a phosphate salt, and on Bentonite or kaolin. The task to be solved was at low concentrations of phosphate as a free-flowing builder Obtain powder in the spray drying process.

The object to be achieved with the present invention was therein, free-flowing, spray-dried, essentially inorganic To create base beads that are only in one finished detergent are transferred to your in Moving surfaces nonionic surfactant, the normally solid, which is sprayed on in a liquid state then is absorbed into the base beads to do so excellent, free-flowing, non-sticky and not to get caking detergent. Object of the invention it was especially to create a product that has so far applied water-soluble silicate is dispensable, and the  Base beads and the detergent compositions made therefrom despite the absence of water-soluble silicate have sufficient mechanical strength and at the same time the undesired deposition of zeolite or zeolite Prevents silicate aggregates on the washed fabrics or is at least reduced. After all, the task was To create products that disintegrate more easily in the wash water and be distributed in it and finally that the carbonate and / or Formulations containing bicarbonate do not contain the presence of materials that prevent gel formation.

The proposed according to the invention for solving these tasks free-flowing, spray-dried hollow spheres, which as Detergent or for the production of particulate present, builders and synthetic nonionic detergent formulations containing organic surfactant can be used because of their bentonite content and a low content of water-soluble silicate or the Absence of silicate in the spray-dried hollow spheres to lower particle deposition on washed fabrics lead are described in claim 1 and contain 5 to 60% by weight water-softening aluminosilicate, 2 to 40% by weight Bentonite, 5 to 60 wt .-% water-soluble builders or one Mixture of such builders, 0 to 30 wt .-% water-soluble synthetic organic detergent and 0 to 5% by weight water-soluble silicate, each with those mentioned in claim 1 Properties. The aluminosilicate is therefore a zeolite an essential exchange capacity for calcium ions, the Bentonite has significant swellability in water and contains one sufficient moisture to break up the platelet to facilitate platelet bonds in it when the hollow beads alone or in a mixture with other detergent ingredients be put in water. The water-soluble builder or the Mixture of builders can be made from a polyphosphate, nitrilotriacetate or carbonate, while no water soluble Silicate is present. The invention also encompasses the use  the hollow spheres for producing detergent compositions by Spray drying the formulation for the hollow spheres with a anionic detergent contained in the Crutcher mixture be obtained or by spraying on nonionic Detergent in liquid form on the  moving hollow spheres free of detergent, or Hollow spheres, which are only a relatively small amount anionic detergent or mixtures of anionic detergent contain. Mixtures of such compositions and mixed anionic nonionic detergent compositions are also useful and can have superior washing properties to lead.

The zeolites used include crystalline, amorphous and mixed crystalline-amorphous zeolites, which Hardness ions in the wash water are satisfactorily quick and sufficient counteract effectively. These are preferably capable Materials react sufficiently quickly with the calcium ions, so that they alone or in cooperation with others Softening agents in the detergent soften the washing water, before these ions mix with other components of the synthetic organic detergent adverse reactions can enter into. The zeolites used are as such characterized that have a high interchangeability for have the calcium ion, from about 200 to 400 or more mg equivalents of calcium carbonate hardness per g of aluminum silicate, preferably from 250 to 350 mg equivalents per g. They also preferably have a softening rate to a residual hardness of 0.02 to 0.05 mg CaCO₃ / l in one Minute, preferably from 0.02 to 0.03 mg / l and less than 0.01 mg / l in 10 minutes, all on anhydrous zeolite based.  

Although other ion exchange zeolites are used can have, usually for the invention Fine-particle synthetic zeolite builders used for the purpose the formula

(NA₂O) _x · (Al₂O₃) _y · (SiO₂) _z · w H₂O,

in which x = 1, y = 0.8-1.2, preferably about 1, z = 1.5-3.5, preferably 2-3 or about 2 and w = 0-9, preferably 2.5-6.

The zeolite should be a monovalent cation-exchanging Be zeolite, d. H. an aluminum silicate of a monovalent Cations, such as sodium, potassium, lithium (if possible) or another alkali metal, ammonium or hydrogen (sometimes). Preferably, the monovalent cation is the one used Zeolite is an alkali metal cation, especially sodium or potassium and especially sodium.

Crystalline types of zeolite, at least partially as good Ion exchangers according to the invention are useful Zeolites with the crystal structures A, X, Y, L, mordenite and erionite, of which types A, X and Y are preferred. Mixtures of these molecular sieve zeolites can also be used especially if zeolite A is present. These  crystalline types of zeolite are known and in particular in "Zeolite Molecular Sieves" by Donald W. Breck, John Wiley & Sons, 1974 described. Typical commercially available Zeolites with the aforementioned structures are in the table 9.6 on pages 747 to 749 of the above Book listed. Some of these and other suitable zeolites are used as builders for detergent compositions in a number of published in recent years Patent specifications described.

The zeolite used in the present invention usually exists made of a synthetic zeolite and is often through a network of substantially equal pores in the range of about 0.3 to 1.0 nm, often characterized by about 0.4 nm (normal), this size being on the unit structure of the zeolite crystal was determined. Type A or one is preferred structure similar to that in particular on page 133 of the above book is described. Good results have been achieved with a 4 A zeolite molecular sieve in which the monovalent Cation of the zeolite is sodium and the pore size of the zeolite is about 0.4 nm. These zeolites are preferred. Zeolite molecular sieves of this type are in the US patent 28 82 243, where it is referred to as zeolite A. are.  

The zeolite molecular sieves with internal exchange ability and water softening properties can be drained in a or calcined form, which are about 0 or contains about 1.5 to 3% moisture, or in a hydrated or water-laden form, the further bound Water in an amount from about 4% to about 36% of the total zeolite weight, depending on the type of used Zeolite. The hydrated form of water containing Zeolite molecular sieve, preferably about 15 to 70% hydrated is preferred for the invention when a crystalline product is used. The production such crystals are known. For example, in manufacturing of the above-mentioned zeolite A, the hydrated zeolite crystals, which form in the crystallization medium, such as water-containing amorphous sodium aluminum silicate gel, without High temperature dehydration used (calcination on a water content of 3% or less that normally in the manufacture of such crystals for catalysts e.g. B. cracking catalysts is used). The crystalline Zeolite is either fully or partially hydrated, can by filtering the crystals from the crystallization medium obtained and in the air at ambient temperatures be dried so that its water content is about 5 to 30%, preferably about 10, 15 to 25%, such as 17 to 22%, e.g. B. 20% is. The moisture content of the zeolite molecular sieve used  however, can be much lower than previously stated. In this case, the zeolite is usually used during the Mixing process and other process steps hydrated.

The zeolite is preferably in a finely divided state, with extreme particle diameters up to 20 µm, e.g. B. 0.005 or 0.01 to 20 µm, in particular from 0.01 to 15 µm, e.g. B. 3 up to 12 µm and especially with an average particle size from 0.1 to 8 µm, e.g. B. 3 to 7 microns in the crystalline state, and from 0.01 to 0.1 µm, e.g. B. 0.01 to 0.05 microns in amorphous Status. Although the outermost particle sizes are much smaller the zeolite particles usually correspond to light Mesh sizes from 0.149 to 0.037 mm, preferably from 0.105 up to 0.044 mm. Develop zeolites with smaller particle sizes often unwanted dust and the larger Particles cannot adequately and satisfactorily the carbonate, bicarbonate, phosphate and / or nitrilotriacetate particles adhere to it along with the bentonite e.g. B. in gel-like form or in the form of a film during spray drying the crutcher mixture to form Hollow beads can be distributed.

The bentonite used is one containing montmorillonite colloidal clay (aluminum silicate). Montmorillonite exists made of a hydrated aluminum silicate, in which about 1/6  the aluminum atoms can be replaced by magnesium atoms, and with which different amounts of hydrogen, sodium, Potassium, calcium, magnesium and other metals loosely linked could be. The for the manufacture of the invention Hollow beads the most useful bentonite clay is that of sodium bentonite or Wyoming or Western Bentonite known who usually from a light to cream colored extremely fine Powder consists of a colloidal suspension in water with strong thixotropic properties. The swelling ability of the clay in water is usually 3 to 15 ml / g, preferably 7 to 15 mg / l, and its viscosity is 6% concentration in water usually in the range of 3 to 30 mPa · s, preferably from 8 to 30 mg / l. Preferred swelling bentonites of this type are under the trademark Mineral colloid commercially available as technical bentonites expelled. With these materials are selected mines and processed bentonite. These materials have 6% Concentration in water has a pH in the range of 8 to 9.4, a maximum free moisture content of about 8% and a specific weight of about 2.6. From the powdered  About 85% pass through a sieve with a quality clear mesh size of 0.074 mm. As part of the invention Composition becomes processed Wyoming Bentonite preferred, although other bentonites can also be used are, especially if they use a smaller proportion of the Form bentonite. Although it is desirable to have the maximum To limit the free moisture content, as mentioned, it is important to ensure that the one used Bentonite has enough free moisture from which it is assumed that the largest part is between adjacent ones Platelets of bentonite are located for rapid decay of bentonite and adjacent materials in the particles relieve if these particles or detergent compositions containing them in contact with water such as wash water to be brought. It was found that at least about 2%, preferably at least 3% and in particular about 4% or more water should be in the bentonite initially, before this with the other components for the hollow spheres is mixed in the crutcher, and this portion should also be present after spray drying. With others Words, over-drying to the point where the bentonite loses its "inner" moisture, the usability significantly reduce the compositions of the invention. If the moisture content in the bentonite is too low, the bentonite does not prevent the formation of silicate zeolite  Agglomerates and does not promote the disintegration of the hollow spheres in the wash water. When the moisture content of the bentonite is satisfactory, he has an interchangeability for calcium oxide from 1 to 1.8% and for magnesium oxide Interchangeability normally 0.04 to 0.41%. Typical chemical analysis values for the materials are: 64.8 to 73.0% SiO₂, 1.4 to 1.8% Al₂O₃, 1.6 to 2.7% MgO, 1.3 to 3.1% CaO, 2.3 to 3.4% Fe₂O₃, 0.8 to 2.8% Na₂O and 0.4 to 7.0% K₂O.

The water-soluble builders or builder salts used or their mixtures can consist of one or more of the conventional materials that exist as builders are proposed or used for such purposes and are in Claim 1 enumerated. they include inorganic and organic builders and their Mixtures. Among the preferred inorganic builders include the various phosphates, preferably polyphosphates, e.g. B. tripolyphosphates and pyrophosphates, such as penta sodium tripolyphosphate and tetrasodium pyrophosphate. Tri sodium nitrilotriacetate (NTA), preferably as a monohydrate is used, as well as other nitrilotriacetates, such as Disodium nitrilotriacetate are preferred water soluble Builders. Sodium tripolyphosphate, sodium pyrophosphate and NTA can be used in hydrated forms, but even when using anhydrous compounds,  the bentonite and zeolite seem to bake during prevent subsequent hydration. Of course make carbonates, such as sodium carbonate, useful builders which can be used as desired, alone or together with bicarbonates such as sodium bicarbonate. However, if not a water-soluble synthetic detergent is present in the hollow spheres according to the invention, bicarbonate is excluded as a builder. If polyphosphates can be used it may be beneficial to use sodium pyrophosphate along with sodium tripolyphosphate in a ratio of 1:10 to 10: 1 and preferably Use 1: 5 to 5: 1, the total of these two Builders is about the same as they are for the Sodium tripolyphosphate is specified. Other water soluble Builders that are considered effective include the various other inorganic and organic phosphates, Borates, e.g. As borax, citrates, gluconates, ethylenediaminetetraacetic acid and iminodiacetate. Preferably, the various builders in the form of their alkali metal salts before, either as sodium or potassium salts or their Mixtures, however the sodium salts are normally preferred. In some cases, e.g. B. if neutral or light acid detergent compositions are prepared can acidic forms of builders, especially organic Builders may be preferred, but the salts are usually either neutral or basic. The silicates, preferably sodium silicate with a Na₂O: SiO₂ ratio in Range from 1: 1.6 to 1: 3.0, preferably 1: 2 to 1: 2.8, e.g. B.  1: 2.35 or 1: 2.4 also serve as builders, because of their strong binding properties and their characteristic Characteristics, aggregates or agglomerates with zeolite particles to promote, however, they represent a special class of Builders, and preferably they are in the invention Compositions not included. However, since it have anti-corrosive properties, which is particularly important is when the detergent solution is in washing machines or other Devices come into contact with aluminum parts, they are sometimes in limited proportions. In these In some cases it may be advantageous to use the hydrated sodium silicate particles add later, so that during of mixing in the crutcher and during spray drying do not react with the zeolite particles or agglomerates form. Although sodium sulfate and sodium chloride as well as others Filler salts have no builder properties they sometimes fillers in detergent compositions used. They don't just increase volume and weight of the product, which facilitates its dimensions, but sometimes also improve stability and physical Properties of the hollow spheres for the detergent composition, into which they are incorporated. Since the invention Compositions even without any fillers are satisfactory, these substances are preferred omitted entirely or their share will be as much as possible  reduced, usually to a practical minimum.

The commonly used detersives are usually either nonionic or anionic or both, but also Amphoteric or amopholytic detergents can be used be, especially together with nonionic and / or anionic detergent ingredients. If anionic detergent Phosphate is used as a water-soluble builder locked out. Cationic detergent ingredients can in the products of the invention as fabric softeners serve. However, they usually don't spray-dried with anionic detergents, as a undesirable mutual reaction can occur. The above Material classes are in the field of detergent active substances well known and have been described repeatedly. Since they are not the preferred components of the invention Represent compositions, an in-depth appears Explanation not required.

Although various nonionic detergents with satisfactory physical properties used , including condensation products from Ethylene oxide and propylene oxide with each other and with hydroxyl groups containing bases, such as nonylphenol and oxo alcohols, it is preferred to use a condensation product from ethylene oxide and higher fatty alcohols than non-ionic Active detergent. In these products, the  higher fatty alcohol 10 to 20 carbon atoms, preferably 12 to 16 carbon atoms and the nonionic detergent contains about 3 to 20 or 30 ethylene oxide groups each Mol, preferably 6 to 12. In particular, there is the nonionic Detergent from one in which the higher fatty alcohol about 12 to 13 or 15 carbon atoms and 6 to Contains 7 or 11 moles of ethylene oxide. These detergent ingredients are available under the trade names Neodol® 23-6.5 and 25.7. To their particularly advantageous properties besides theirs good cleaning effect with regard to oily stains on the washing materials include a relatively low one Melting point, however, is noticeably above room temperature lies so that it is sprayed as a liquid on the hollow spheres can be, which then solidifies.

Various anionic detersives, usually used in the form of sodium salts, most advantageously however, linear higher alkylbenzenesulfonates are higher Alkyl sulfates and higher fatty alcohol polyethoxylate sulfates. The higher alkylbenzenesulfonates are preferably less than Sodium salt before and contain a linear alkyl group 12 to 15, e.g. B. 13 carbon atoms. The alkyl sulfate is preferably a higher fatty alkyl sulfate with 10 to 18 carbon atoms, preferably 12 to 16 carbon atoms, e.g. B.  12 and is also used in the form of the sodium salt. The higher alkyl ethoxamer sulfates contain similar ones Way 10 or 12 to 18 carbon atoms, e.g. B. 12 in the higher alkyl group, preferably a fatty alkyl group and their ethoxy content is usually 3 to 30 Ethoxy groups per mole, preferably 3 or 5 to 20. Here too the sodium salts are preferred. So the alkyl groups are preferably linear and represent fatty alkyl groups with 10 to 18 carbon atoms, the cation is preferred Sodium, and if a polyethoxy chain is present the sulfate group at its end. Other useful anionic Detergent actives include the higher olefin sulfonates and Paraffin sulfonates, e.g. B. in the form of their sodium salts, the Olefin or paraffin groups contain 10 to 18 carbon atoms. Specific examples of preferred detergent ingredients are sodium tridecylbenzenesulfonate, sodium tallow alcohol polyethoxy (3EtO) sulfate and hydrogenated tallow alcohol sulfate in Form of the sodium salt. Except for the preferred ones anionic detersives can be other substances of this known group may also be present, particularly in a smaller proportion with respect to those described above. Mixtures can also be used, and in some Cases are these mixtures of the individual washing active ingredients think. The different anionic detergents are well known and by Schwartz, Perry and Berch  in Suface Active Agents and Detergents, Volume II, 1958, Interscience Publishers, Inc.

In the crutcher mixture from which the hollow spheres or the Detergent compositions can be spray dried, can contain various auxiliaries, or these Excipients can be added later, which is often the case through the physical properties of the excipient, its resistance to high temperatures, its resistance to decomposition in the aqueous crutch medium and its volatility is determined. To the more important ones Auxiliary materials include a polyacrylate, which is suitable for the Control the properties of the hollow spheres and theirs Bulk weight has proven useful, dispersing properties possesses, in the compositions according to the invention counteracts a deposit as well as a new deposit and helps make the crutcher mixture flowable and keep it homogeneous.

That in the preferred hollow spheres according to the invention contained polyacrylate has a low molecular weight, usually in the range of about 1000 to 5000, preferably from 1000 to 3000 and in particular from 1000 to 2000 or of about 2000. The polyacrylate can be partial or complete be neutralized, e.g. B. about half or one  Thirds are present as sodium polyacrylate. Although modified Polyacrylates instead of the described sodium polyacrylate can be used, including some others Alkali metal polyacrylates and hydroxylated polyacrylates, such a replacement is preferably to a lesser one Limited proportion, and preferably the polyacrylate from an unsubstituted sodium polyacrylate. These materials are under the label Alcosperse® available. The sodium polyacrylates are available as clear amber liquids or powders, the solutions having a solids content of about 25 to 40%, e.g. B. 30% and the pH of these solutions or a 30% aqueous solution of the powder about 7.5 to 9.5, e.g. B. is about 9. These materials are complete in water soluble and have already been used as dispersants. It has been shown to have the ability to bind possess calcium ions and used them to deposit insoluble calcium compounds from aqueous solutions to prevent. Small quantities or help with spray drying Percentages, the resulting hollow spheres have higher porosity to rent.

If the crutcher mixture is a carbonate and / or bicarbonate and contains silicate, the mixture may tend to be a gel to form or "freeze" in the crutcher, even if the  Amount of silicate is low, especially if due to Delays in processing make the crutch mix longer than the normal 30 minutes or so held in the crutcher becomes. In such cases, the presence of silicate in the mixture preferably promoting processing Means are used, which accordingly in the finished Hollow beads and contained in the detergent composition are to premature solidification or gelation to prevent. These agents are preferably citric acid and magnesium sulfate. Instead of citric acid can use soluble citrates, such as sodium citrate will. While anhydrous magnesium sulfate is preferred, however, various hydrates of magnesium sulfate, how to use epsom salts. Magnesium citrate can also be used. Instead of the preferred, gelation preventive system can other means and appropriate Systems are used to make the crutcher mixture flowable such as sodium sesquicarbonate instead of a Part of the sodium carbonate and sodium bicarbonate used can be. These are processing-promoting Means useful in many cases, but it is a feature of the invention that they are for the preparation of the preferred Hollow beads that do not contain silicate are not required will.  

Some auxiliaries, such as fluorescent brighteners, pigments, e.g. B. Ultramarine blue, titanium dioxide and inorganic filler salts can be put in the crutcher while others like Perfumes, enzymes, bleach, some coloring substances, Bactericides, fungicides, fabric softeners and fluidity promotional products are often sprayed onto the hollow spheres or in another way with the hollow spheres or the spray-dried Detergent composition are mixed together with a nonionic detergent and / or independently of it so that it is affected by the elevated temperatures are not affected during spray drying and their presence in the spray-dried hollow spheres the absorption of the nonionic detergent is not inhibits when sprayed onto the hollow spheres. Resistant and normally solid auxiliaries can, however be mixed into the starting mixture in the crutcher. So it is envisaged that pigments and fluorescent brighteners, provided used, usually included in the crutch mix from which the hollow spheres are spray dried. The preferred dye is ultramarine blue, however others can resistant pigments and dyes together with it or be used in its place.

Since the spray-dried hollow spheres according to the invention sometimes cannot have an attractive color, usually  due to the use of naturally occurring minerals, the color tone of the dye can be adversely affected. It has been found that the incorporation of a minor Amount of titanium dioxide in the crutcher mixture helps to get the one you want Maintain hue of the dye. The presence of titanium dioxide does not appear to have an adverse effect on that Have appearance of laundry with detergent compositions on the basis of hollow spheres containing titanium dioxide was washed.

The preferred fluorescent brighteners include disodium 4,4′-bis (4-anilino-6- (2 ″ -hydroxyethyl) methylamino-s-triazin-2-yl-amino) -2,2 -′- stilbene disulfonate (Tinopal 5BM®), especially in an extra concentrated form. However, it can also various other cotton brighteners, e.g. B. the sometimes referred to as CC / DAS brightener used by Reaction product from cyanuric chloride and the disodium salt derived from diaminostilbene-disulfonic acid, including Modifications to the substituents on the triazine ring and the aromatic rings. This brightener class is known in the field of detergents and is mostly used used when there are no bleaches in the end product are. When bleaches are present, such as sodium perborate or other oxidizing bleaches, are common brighteners resistant to these bleaches in the Crutcher mixture incorporated. These include the benzidine sulfone disulfonic acids, Naphtholtriazolylstilbenesulfonic acids  and benzimidazolyl derivatives, polyamide brighteners, which are also may be present include aminocoumarin or diphenylpyrazoline derivatives, and polyester brighteners, which are also can include naphthotriazolylstilbenes. These brighteners are usually in the form of their soluble Salts used, but can also be added as acids. The cotton brighteners usually contain larger amounts on brightener systems.

Enzyme preparations that are normally added to the hollow spheres given because they are sensitive to heat, can be made from a variety of commercially available products to be chosen, the most common being the alkaline proteases be applied. Amolytic enzymes, such as α-amylase can be used. The preparations mentioned contain usually active enzymes together with an inert one powdery carrier, such as sodium or calcium sulfate, and the The amount of active enzyme can vary widely, usually from 2 to 80% in the commercial product. Present refer to the stated amounts on enzyme preparations and not on their active ingredient. The perfumes used, the usual are sensitive to heat and contain volatile components  can, including a solvent such as alcohol, are usually synthetic substances, sometimes mixed with natural components. Generally included they alcohols, aldehydes, terpenes, fixatives and others normal perfume components. In the present case they are Flow promoting agents such as special clays that sometimes added to detergent products because they are often improve fluidity and stickiness of various Reduce compositions, unnecessarily, possibly partly due to the presence of the bentonite and the absence or the very limited amount of silicate. You can however, if desired, can be added to improve fluidity continue to improve. It has been found that that out the detergent compositions produced according to the hollow spheres according to the invention do not require any anti-corrosive additives replace the omitted silicate, but it is in the frame the invention to use suitable such materials, and it is preferred to use those which meet the conditions in the crutcher and in the spray tower. Such anti-corrosive additives or anti-oxidants can be organic or inorganic, the inorganic Materials are usually preferred. you will be in particular on their suitability for preventing corrosion of aluminum parts selected in washing machines. If it is desirable to continue to use a silicate for this purpose  use, or due to its interchangeability for water hardness causing magnesium ions, powdery silicate normally preferred, such as water-containing sodium silicate, which is commercially available under the name Britesil® and a Na₂O: SiO₂ ratio of 1: 2.4. This silicate is preferred added later. But others can usually solid soluble silicates, preferably of alkali metals, subsequently to the hollow spheres according to the invention be given, preferably after absorption of the nonionic Active detergent.

If the product has fabric softening properties plasticizers, preferably in dry powder form subsequently to the hollow spheres in a suitable manner are given. This class of substances is known and mostly these plasticizers are cationic compounds, in particular quaternary ammonium compounds, such as quaternary ammonium halides. The quaternary ammonium chloride is particularly preferred and bromides with higher alkyl, alkylaryl and Arylalkyl-lower alkyl groups such as distearyl dimethyl ammonium chloride. Of the commercially available plasticizers especially that under the trade name Arosurf TA-100® displaced preferred.  These compounds also have antistatic and antibacterial activity, but can, if desired, other antibacterial adjuvants are also used which are preferably added subsequently.

Of course there is water in the crutcher, which as Medium for the dispersion of the various components serves for the hollow spheres, and there is also a lot in the product Contain water, both in free form and in hydrate form. During the drying of the hollow spheres their initial moisture content, which is approximately 25 to 60%, reduced to about 5 to 15%, which is sufficient that at least the bentonite in the dried hollow spheres Contains 2% and preferably at least 4% moisture. Deionized water is preferably used so that the content of ions causing hardness is very low and metal ions that decompose organic materials in the crutch mixture, the hollow spheres and the resulting ones favor manufactured detergent compositions on a minimum quantity is reduced. However, urban or tap water can be used. Usually is the hardness of the water less than 150 ppm as CaCO₃, preferably less than 100 ppm and especially less than 50 ppm.

The proportions of the various components in the hollow spheres and the spray dried detergent composition  are set so that the hollow spheres flow freely and sufficient absorption capacity for the non-ionic Have detergent active in the liquid state on it is applied so that the detergent compositions are satisfactorily free flowing. Of course the detergent compositions provide effective cleaning agents represents, with the builders the cleaning effect of organic detergent active in aqueous solutions. It is important that the products obtained are not too unwanted deposits of zeolite particles (or zeolite Silicate aggregates) on the washed materials. The zeolite particles and the bentonite particles discolor, though they are insoluble, the laundry is not undesirable Way or lighten colored laundry because of their particle sizes are very small, but such discoloration can occur if zeolite aggregates are formed that are sufficient are great that they are held on the tissues and by the eye easily perceived, especially when essential Do not share this with the drying air during of automatic drying removed from the washed laundry will. It is also desirable that the hollow spheres and the detergent compositions made therefrom have an appropriate bulk density and attractive color.  

The spray-dried hollow spheres preferably contain 3 to 15% by weight of moisture, in particular 5 to 12% by weight and usually 7 to 10% by weight, any water of hydration included. Such Water of hydration can be found in zeolite, NTA, phosphate, Carbonate, bicarbonate and magnesium sulfate may be present, in addition to that between the plates of bentonite. The specified moisture content even includes strongly bound hydration water, e.g. B. such that the zeolite itself after several hours Distilling a toluene dispersion is retained. In some cases, when the concentration of the zeolite in the Product is high, so that up to about 12 to 15% moisture could be contained in the zeolite as water of hydration, the moisture content in the spray-dried hollow beads even 20% and occasionally up to about 25%. Usually, to achieve good flowability  of the product and for the greatest possible reduction of stickiness and lump formation, however, the upper limit about 15%, especially if the final detergent composition a noticeable amount of nonionic detergent contains. The stated percentage of zeolite closes the hydration water contained in it. It is also possible, usable spray-dried hollow spheres with moisture contents less than 3%, provided The bentonite contains sufficient for the reasons given above Water. Because of the strong attraction of moisture through the zeolite and the mode of action of the others hydratable materials that may be present however, it has usually been found that a minimum of 3% Moisture is needed to make a loss of the desired to avoid internal moisture of the bentonite, which the Seems to "smear" platelets and facilitate their separation, if a product containing this bentonite in water is dispersed. When making anhydrous products, tend to, even if there is sufficient moisture in the Bentonite is retained, causing physical instability, form lighter powder and are subject to abrasion and Decay.

The bulk density of the spray-dried hollow spheres can are in the range of 0.2 to 0.9 g / cm³. Bulk weights in the  lower part of this area are easier to get to, though the crutch mixture to be spray-dried contains no silicate, and if little or no nonionic detergent of the beads is absorbed. The higher bulk weights are obtained when nonionic detergent is on the porous bead is applied and some silicate is contained in the beads. Have the lighter products Bulk weights in the range of 0.2 to 0.5 g / cm³, often from 0.3 to 0.4 g / cm³, while the bulk weights of the heavier Particles in the range of 0.6 to 0.9 g / cm³ and usual are in the range of 0.6 to 0.8 g / cm³. The particle sizes the balls usually correspond to a clear mesh size from 2.00 mm to 0.149 mm, d. H. they pass through a sieve with a mesh size of 2.00 mm and stay on a sieve with a mesh size of 0.149 mm. They preferably correspond to a mesh size of 2.00 mm up to 0.25 mm. The ratio lies in preferred formulations Bentonite to zeolite in the range 1: 4 to 1: 1, the ratio water-soluble builders to zeolite in the range 1: 2 up to 3: 1 and the ratio of bentonite to water-soluble builders in the range 1:10 to 1: 1 Ranges the following values: 1: 3 to 2: 3; 2: 3 to 2: 1 or 1: 6 to 1: 2. Expressed in percentages, the compositions contain preferably 10 to 40% partially hydrated Sodium zeolite, preferably 15 to 25 wt .-% water of hydration  contains and the exchangeability for calcium ions from 200 to 400 milligram equivalent calcium carbonate hardness per g of anhydrous zeolite has 2 to 35% bentonite with a swellability of 7 to 15 ml / g and a viscosity from 8 to 30 mPa · s at 6% concentration in Water, 10 to 50% water-soluble alkali metal builder salts or of their mixtures, 0 to 25% water-soluble synthetic anionic organic detergent and 0 to 3% water-soluble silicate, which, if present, is made of an alkali metal silicate with an alkali metal oxide: silicon dioxide Ratio in the range of 1: 1.6 to 1: 3, especially from 1: 2 to 1: 2.8. Preferred formulations of the Hollow beads contain 15 to 35% zeolite A, 5 to 20% processed Wyoming bentonite, 20 to 50% water soluble Sodium builder salts or mixtures thereof, 0 to 20% water soluble synthetic anionic organic detergent and 0% sodium silicate.

Although carbonate and bicarbonate builders for manufacturing the hollow spheres according to the invention are useful, especially those on the nonionic detergent should be sprayed, polyphosphate and / or nitrilotriacetate  Builders often for the spray-dried hollow spheres preferred regardless whether it is intended apply nonionic detergent to them or Not. Preferred formulations of the hollow spheres on the Basis of NTA as the only or main builder contain 15 to 35 or 40% hydrated zeolite, 5 or 10 to 20% bentonite and 20 to 50 or 60% NTA. When a Phosphate such as sodium tripolyphosphate the main water soluble Builders can represent the same proportions on zeolite and bentonite can be used, however usually more phosphate (than NTA). Preferably is used for such hollow spheres, on the nonionic detergent should be sprayed on or for comparable compositions based on carbonate, no water-soluble synthetic organic Active detergent and little or no water-soluble Silicate used. If carbonate is used in such formulations, its amount usually 10 to 30%.  

If an anionic detergent or another suitable Organic detergent active in the crutcher mixture is given, its shares make up 3 or 5 to 30% preferably 5 to 25% and in particular 10 to 25%, e.g. B. 10 or 15% of the product, with the detergent pre preferably a sodium alkylbenzenesulfonate with linear, 10 to 18 and in particular containing 12 to 16 carbon atoms Alkyl group, a sodium fatty alcohol sulfate, its alcohol Contains 10 to 18 carbon atoms or a sodium fatty is alcohol ethoxylate sulfate, the fatty alcohol of 10 to 18 Koh lenstoffatome contains and the 3 to 30 ethylene oxide groups per mole. Mixtures of these washing active ingredients can also be used. Currently, the most preferred is wash active Sodium tridecylbenzenesulfonate with linear alkyl group.

If a nonionic detergent from the spray dry is not absorbed (sometimes a small one can Portion absorbed into the interior of the spray-dried particles amount) is usually in the range of 5 or 8 to 30%, preferably from 10 to 25%, e.g. B. at 15 or 20%. In these cases the preferred is nonionic Detergent active is a condensation product of 6 to 12 moles Ethylene oxide and one mole of a higher fatty alcohol with 12 up to 16 carbon atoms.  

If there is a polyacrylate in or out of the hollow spheres Detergent to be made makes up its amount normally 0.5 to 1% and its molecular weight be preferably carries 1000 to 5000.

Since the presence of anionic detergent in the spray dried spheres the formation of a hollow sphere structure, which is a desired amount of nonionic detergent is able to absorb, inhibit, it can be advantageous spray-dried laundry detergent and make them with balls Chen to mix on the nonionic detergent was sprayed on, so that the proportion of nonionic washing active ingredient in the final product can be larger. For this you can varying ratio ranges are applied, e.g. B. 1:10 to 10: 1, 1: 5 to 5: 1 and 1: 2 to 2: 1 of the mentioned components depending on the desired properties of the end product. The bulk density of the beads should be before mixing be about the same, preferably within 0.1 g / cm³, as well as the particle sizes that one normally has Mesh sizes from 2.00 mm to 0.149 mm correspond to one Pour through and separate into the final mix too prevent.

The proportions of auxiliaries and that promote processing the substances in the hollow spheres and in the spray-dried  Detergents are usually limited to 20%, preferably point to 1 to 10% and in particular 3 to 7%. The Proportions of substances promoting processing amount to if magnesium sulfate and citric acid are used, normally 0.5 to 2% magnesium sulfate, preferably 1 to 1.5%, and 0.1 to 0.5% sodium nitrate, preferably 0.1 to 0.3%. When using coloring substances, pigments and Fluorescence brighteners usually make their proportions 0.05 to 0.6% coloring pigment, such as ultramarine blue, preferably 0.2 to 0.4% and 0.1 to 4% fluorescent brighteners, preferably 1 to 3%. The proportion of titanium dioxide as whitening pigment is usually 1 to 3% preferably 1.5 to 2.5%. If instead of a coloring pig one or more dyes are used the amounts of which are usually 1 to 50%, in particular 5 to 20% the amount of coloring pigment.

The bulk density of the preferred spray-dried hollow beads Chen according to the invention, the NTA or polyphosphate scaffold fabrics, or any of the preferred water-soluble preferred above Builder salts can range from 0.2 to 0.8 g / cm³, the aluminosilicate consists of hydrated Zeolite A, the bentonite contains at least 3% moisture,  based on the anhydrous bentonite, the water-soluble If it is present, silicate is sodium silicate a Na₂O: SiO₂ ratio in the range of 1: 2 to 1: 2.8 and the moisture content of the beads is 3 to 12%. If the beads contain NTA or another sodium salt of Ni trilotriacetic acid with or without synthetic organic Containing detergent, the ratio is bentonite: Zeolite 1: 6 to 1: 2, the ratio NTA: zeolite 1: 2 to 2: 1 and the ratio bentonite: NTA 1: 6 to 1: 2. The percentages on hydrated zeolite, bentonite, sodium nitrilotriacetate or silicate are in the range of 10 to 40%; 2 to 25%; 10 to 40% or 0 to 5%.

If the preferred NTA-containing beads also have one synthetic anionic organic detergent together with zeolite A, bentonite and moisture as well as given if contains soluble silicate, the amount of synthe table anionic organic detergent preferred show 5 to 30%. It consists of sodium alkylbenzenesulfo nat with linear, containing 10 to 18 carbon atoms Alkyl group, a sodium fatty alcohol sulfate, its alcohol Contains 10 to 18 carbon atoms, or a sodium fat alcohol ethoxylate sulfate, the fatty alcohol of 10 to 18 carbons has atoms and the 3 to 30 ethylene oxide groups each Mol contains, or from mixtures of 2 or more of these  Active detergents. The water-soluble builder salt is a Sodium salt of nitrilotriacetic acid (NTA), the ratio Bentonite: zeolite is 1: 6 to 1: 1, the ratio NTA: Zeolite 1: 3 to 3: 1, the ratio bentonite: NTA 1:10 to 1: 1 and the ratio of synthetic anionic organic Detergent: Zeolite 1: 1 to 1: 4. The percentages of hy hydrated zeolite, bentonite, sodium nitrilotriacetate, synthetic anionic organic detergent and Silicate make 10 to 40%, 2 to 25%, 10 to 40%, 10 to 25% (preferred range) or 0 to 5%.

For hollow spheres containing phosphate when pentasodium tri polyphosphate or tetrasodium pyrophosphate or their mixture used instead of NTA are (without synthetic detergent) the materials and ratio se the same as for the corresponding NTA containing Beads, but the percentages are 15 to 35%, 5 to 20% or 15 to 40%. The quantities parts of the various components in the base hollow  beads of final detergent composition, if nonionic detergent, optionally together subsequently applied with other materials can easily be calculated from the values given for the hollow spheres NEN, if you consider the proportion of detergent and the other deducts subsequent added materials. Vice versa can be from the formulation of the final product in proportions of the components contained in the hollow spheres and use these to calculate the Crutcher mix. If e.g. B. for the final detergent composition only nonio African detergent was added so that the Endpro product contains 20% non-ionic detergent, let itself out of the different, for the components in the hollow spheres specified areas in the final Calculate the detergent product if the former is 0.8, d. H. (100-20) / 100 multiplied. Similarly, is the multiplier 0.92 to 0.75 if the proportion of the nonio African detergent in formulations in which only this additive was added to the hollow spheres, 8 to 25 % of the detergent composition. The final one Percentage of nonionic detergent in the product makes up 8 to 30%, preferably 10 to 25% and especially 15 to 22%, e.g. B. about 20%. In some cases and at 8 to 13% may be preferred for certain types of products. Usually the percentage of perfume in the end product  0.1 to 1%, preferably 0.2 to 0.4% of the percentage of enzyme 0.5 to 3%, preferably 1 to 2%, and, if water-containing sodium silicate is added subsequently, its amount is usually not less than 1% and is preferably limited to about 5%, although in some cases len up to 10% can be used. If a fabric softener contained in the final product usually makes up its amount 3 to 12% and preferably 5 to 10%.

The hollow spheres and detergent compositions according to the invention are made from an aqueous crutcher mixture spray dried, which is usually about 40 to about Contains 70 to 75% and preferably 50 to 65% solids, the rest being water, preferably deionized water as stated before, but also city water be used. The crutcher mixture is preferred by successively adding the different components manufactured in such a way that the most miscible, easily pumpable and non-settling slurry for spray drying is obtained. The order of addition the materials can be varied depending on the circumstances, however, if used, the silicate solution should last and if not last, at least after adding one Gel formation or a combination that prevents "freezing" of additives or processing aids,  such as citric acid and magnesium sulfate. Usually if you prefer, all or almost all of the water first in the crutcher, preferably at about Processing temperature, whereupon use if necessary ten, processing funds and others in small components, including pigment, Fluorescent brightener and polyacrylate, if used, too be added, and then the zeolite, the water-soluble Ge builder, the anionic detergent, if used, the bentonite and the silicate, if used. Usually wiord each component carefully with these additions mixes before adding the next component, however the type of addition may vary depending on the circumstances the so that, if feasible, common additions are possible are. Sometimes adding one component in two or more shares are made and sometimes different Components are premixed before adding to the mix accelerate process. Usually the mixge speed and the mixing power with the addition of materials elevated. For example, until after adding the last one Zeolite or soluble builders low mixing speed abilities are applied, whereupon the mixing speed brought to a medium and then to a high value on which it is preferably before, during and after the Addition of the silicate solution is kept.  

The temperature of the aqueous medium in the crutcher is usually around room temperature or is elevated. Usually it is in the range from 20 to 80 ° C., preferably from 30 up to 75 or 80 ° C and in particular from 40 to 70 ° C. The he Heating the crutch medium can dissolve the water favor the salts in the mixture and thereby the Improve miscibility, but heating in the crutcher can reduce production speeds and sometimes promote settling of the mixture. An advantage of using it the processing-promoting substances in the mixture, especially if soluble silicate is present in that both at higher and lower temp mature slurries are obtained which do not form a gel. Temperatures of over 80 ° C and sometimes over 70 ° C will be usually avoided because at these temperatures a or several components of the crutch mixture, e.g. B. sodium can add bicarbonate. In some cases, increase too lower Crutcher temperatures are the upper limit for the Solid content in the crutcher, probably because it is more normal wise gel-forming or settling component insoluble will.

The mixing times in the crutcher to achieve good slurries gene can vary widely, from just 5 minutes in small Crushers and slurries with higher moisture  content up to 4 hours in some cases. The required Mixing time until all components of the Crutcher mixture are mixed are mixed homogeneously in a medium, can only take 10 minutes to an hour in some cases although 30 minutes is the preferred upper limit are. Including the initial mixing times be the time in the crutcher is usually 15 minutes to 2 Hours, e.g. B. 20 minutes to 1 hour, but should Crutcher mixture must be mobile for at least 1 hour, do not gel or settle, preferably 2 hours after and in particular 4 hours or more after the end ter preparation of the mixture. It is preferably 10 to 30 hours agile until pumped out into the spray tower will allow situations where other manufacturing problems arise, can be taken into account.

The crutcher slurry containing the various salts and other components dissolved or in particle form evenly contains distributed, becomes a spray skirt in the usual way lead tower, which is usually near the crutcher located. The slurry is from the bottom of the crusher too a displacement pump, which they run at high pressure through spray nozzles at the top of one in counterflow or DC operated conventional spray tower in which the Droplets of the slurry through a hot drying gas,  usually the combustion products of heating oil or natural gas fall, are dried to the desired hollow spheres. During the drying process, some of the which bicarbonate with the release of carbon dioxide in Car bonat can be converted together with in the spray drying mixture containing polyacrylate the physika properties of the resulting hollow spheres sert so that they have greater absorbency for liquids possess such as liquid nonionic detergent, which can then be sprayed on them. The Zeo lith, the bentonite and the polyphosphate, if present, also seem to absorb liquid and promote the formation of solid spheres. The poly acrylate improves the properties of the beads and leads also to faster drying, which increases throughput is raised by the tower.

After drying, the product will be of the desired size from Z. B. 2.00 to 0.25 mm or 0.149 mm and is then active for spraying on the nonionic washing ready when it comes from a basic formulation was put, the hollow beads in warm or on Room temperature cooled state can be present. Usually However, the nonionic detergent active is increased Temperature of z. B. 30 to 60 ° C, such as 50 ° C heated to  ensure that it is liquid. When cooling down to room temperature it solidifies in an undesirable manner and often forms a waxy solid. Even at room temperature the nonionic detergent somewhat sticky, but what does not result in the final composition has low fluidity because the detergent under or penetrates the surface of the hollow spheres. The not ionic detergent active in the form of a spray or from droplets in a known manner to the moving or vice versa Rolled hollow spheres is preferably applied from the condensation product of ethylene oxide and higher Fatty alcohols as previously indicated. However, it can also other nonionic detergents can be used. The Enzyme preparation, which is referred to herein as an enzyme, although it also contains carrier material that contains water Silicate and other powdery auxiliaries can be on the part be dusted off while the perfume and others after liquids to be added at a suitable time be sprayed on before or after adding the powder can.

The spray-dried detergent, the spray-dried hollow beads and the detergent made from them together Settlements contain little or no silicate from the crutcher mixture, although some silicate in solid form afterwards  can be added. The subsequently added powdery Silicate, when used, does not seem to have much with it react the zeolite so that zeolite silicate agglomerates, that tend to deposit on washed items, compared to deposits from products containing silicate had been added in the crutcher. Although without existing bentonite silicate usually because of its influencing the properties of the hollow spheres and ner anticorrosive effect is used, the result lying formulation acceptable hollow spheres and cause no corrosion of aluminum objects. Also affected Bentonite does not affect the durability of the product and actually seems to be helping to make the beads are held together so that they are against breaking and Resist powder formation during transportation and use are dig. The bentonite significantly improves the properties final composition, leads to a stronger one Calcium ion binding and reduced deposition of zeolite on the washed fabrics. If polyacrylate with low molecular weight are the hollow gel porous and better absorb the liquid in liquid was present nonionic detergent without reduce the bulk weight of the product in an impermissible manner is gert. When you consider that bentonite is a clay is and serves as a binding agent, one would have deposits and  Have to expect gelling problems. The reduced waste less gelation and easy dispersion of the product are therefore surprising. It is also important, that the presence of the small amount of polyacrylate in the spray-dried beads into a better spray skirt Base beads and detergent compositions leads to an improved absorption of the liquid non-ionic detergent through the base beads chen.

The following examples illustrate the invention. Provided nothing else is indicated in the examples and in the description all temperatures ° C and all parts are parts by weight. If for the zeolite weights and ratios nisse are given, they refer to the normal Hydrate, since it is assumed that the water of hydration of the Zeo liths not leaving the zeolite and not part of the aqueous Medium in the Crutcher mixes. There is also a part of the water in the hollow spheres and in the detergent together the water of hydration of the zeolite. In Similarly, the moisture associated with the bentonite becomes moist not considered free moisture. Because of this difference is made up of its lower percentage often neglected for practical reasons.  

Example 1 (comparative example)

Spray a crutcher batch of 100 parts for manufacture dried base beads, which are considered satisfactory for the subsequent transfer into a detergent together settlement by adding synthetic non-ionic orga African active detergent is considered in the following Manufactured in this way: 47 parts of deionized water with a Temperature of about 27 ° C and then successively and initially with 1.4 parts Tinopal 5BM Extra Conc.®, 0.13 parts Ultramarine Blue Powder, 0.07 part sodium polyacrylate, 21.11 parts of hydrated zeolite 4A (20% crystall water), 6.25 parts bentonite, 23.49 parts Sodium carbonate (natural anhydrous soda) and 0.91 Parts of titanium dioxide mixed together. During the Mixing the various components together becomes the mix speed on a medium and finally on a high value increases, and after adding all the ingredients, which takes about 15 minutes will become another one mixed for another hour (in some cases, up to 4 hours be mixed). During this time, part of the pre available water, e.g. B. about 2 to 6 parts of water by Ver vapors are lost and, if desired, replaced. The crutcher slurry is constant during mixing  flexible, does not form a gel, does not settle or bakes.

About 5 minutes after all components of the crutch mixture are mixed in, the mixture from the crutcher into a Pump led, which they in at a pressure of about 20.6 bar the top of a counter-current spray drying tower with an initial temperature of around 430 ° C and one Brings final temperature of about 105 ° C. The educated, in essentially hollow balls made of inorganic material Chen have a bulk density of about 0.6 to 0.7 g / cm³ initial tack below 10%, particle sizes in an area that is essentially an internal mesh size from 2.00 mm to 0.25 mm corresponds (they are on this Be richly sieved) and a fine substance content, which a sieve with a clear mesh size of 0.297 mm, about 15%. The moisture content of the beads is 1 to 10% and is usually closer to 10%, e.g. B. at 8 to 10%. The spheres formed are free-flowing (flow rate 80%) non-sticky, satisfactory porous and yet have a solid surface. They easily absorb essential ones Amounts of liquid nonionic detergent without in  undesirably becoming sticky.

The spray-dried beads become detergent products te made by moving the moving surfaces of the Beads a normally waxy nonionic Sprayed active detergent. Neodol 23-6.5® is used, however also Neodol 23-7® or Neodol 25-7® (and sometimes Neodol 45-11®) can be used. The non-ionic detergent is in the heated liquid state with a temp temperature of around 45 ° C. It is consumed in such an amount sprays that the final product about 20% non-ionic washing ac contains active substance. Proteolytic enzyme is in powder form in a concentration of about 1.5% of the product is applied, and perfume is in one Amount sprayed on that its concentration is 0.25% of the product is. The detergent compositions obtained have a bulk density of about 0.7 to 0.8 g / ml and contain about 32.45% zeolite (hydrated), 19.7% non-ionic active detergent, 32.0% sodium carbonate, 1.3% free water, 1.4% enzyme, 1.6% fluorescent brightener, 0.25% perfume, 0.2% ultramarine Blue, 9.6% bentonite, 0.1% sodium polyacrylate and 1.4% Titanium dioxide.  

The detergent of the above formulation provides is an excellent detergent and is suitable for especially for washing household laundry in automatic Washing machines. It is physically and aesthetically appealing due to the fact that it is not dusty and flows extremely freely, so that it is in glass and plastic bottles with a narrow neck can be filled from which it can be easily measured can. The detergent compositions containing bentonite genes have, as indicated, an improved binding capacity for calcium ions, but more importantly, let them less zeolite residue on laundry returned with them in an automatic washing machine at the usual concentrations trations of such products and normal washing temperatures was washed, especially if the laundry was on a line was dried as similar compositions with less Bentonite and with sodium silicate in the spray dried Globules. This difference is even more pronounced, though the wash water is very hard, e.g. B. a hardness of 200 ppm. than has calcium carbonate, the wash water is cold and a Washer-proof was applied.

The base hollow spheres and the washing made from them agent compositions are acceptable standard products compared to the other hollow spheres and detergent together of the following examples with which they are presented in  are comparable in some ways. Even the manufacturing procedures are essentially the same and are called considered satisfactory.

Using the normal procedure, Crutchermi can be made quickly, sometimes in just 5 minutes, and can be pumped out of the crutcher just as quickly, sometimes in only 10 minutes. However, it is often important that the inventor Mixtures according to the invention in the crutcher for at least 1 hour can remain without forming a gel or solidifying gene, because sometimes in the technical production malfunctions of such periods of time occur. The described crutcher The mixture can be kept in the crutcher for up to 4 hours and often noticeably longer without forming a gel or to solidify, which is at least partly due to the content Bentonite and the absence of silicate is attributed. This effect of the bentonite is surprising because it affects the Crutcher mixture has a thickening effect, but although the mixture can be thickened noticeably, it remains pumpable. The Crutchermi components used in smaller quantities such as fluorescent brighteners and pigments can be left out as well as the enzyme and perfume, although preferred will include all of these materials in the final product are. The temperature of the crutch mixture can be modified e.g. B. be increased to 52 ° C, and the proportions of the various  NEN components can be within the Be ranges can be varied by ± 10%, ± 20% and ± 30%, however editable mixtures are obtained that correspond to the desired th hollow beads and detergent compositions. The solids content in the Crutcher mixture can also exceed the specified range can be varied, e.g. B. to 45% and 65%, with good mixing and spray drying achieved becomes. There may be other orders in the addition of the Components are applied to the crutcher, however it is usually desired, any silicate last or against End add, and preferably the bentonite added at a late stage in the proceedings, in particular right in front of the silicate. Instead of zeolite 4A X and Y zeolites are used, as well as other zeolites A species, preferably about 80% hydrated te zeolite 4A (moisture content about 20%) of this example used, but are different degrees of hydration of the zeolite is acceptable and in some cases can be nearly Use anhydrous crystalline zeolites or amorphous zeolites be det. The variation in the amount of bentonite within the specified range on z. B. 7%, 13% and 19% in the Base hollow beads still give usable products, however, the larger proportions of bentonite are included the prevention of half-zeolite deposits on the laundry usually more effective. In some cases it may be desirable  within the ranges specified in the description use higher percentages of bentonite, being careful care must be taken that the other components of the base hollow spheres are present so that the spheres flow freely and are effective cleaning agents. The share of in the Bentonite suitable for commercial products depends on a number of factors, and usually lies in the Midway between desired reduction in zeolite backlog des and desired builders and other functional Properties of the other components of the detergent together settlement, which instead of an increased amount of bentonite could be processed.

With the detergent composition of this example, the less residue on washed laundry lets, improvement is achieved by examining the be product compared to a control product with essentially the same wording, that contains no bentonite and about 8% sodium silicate. For this review will be a Whirlpool Suds Saver model wash machine used, with washing periods of 8 minutes at a time mild wash cycle. The concentration of detergent together setting is 0.06%, the wash water has a mixed Calcium-magnesium hardness of a total of 200 ppm as calcium carbonate and the temperature of the water is 24 ° C. Ge  were washed: 100% cotton; 100% polyester; 85% Acetate + 15% nylon and 65% polyester + 35% cotton. The laundry got wet and after drying on the line rated (drying on a line usually leads to visible residues as drying in an automa table dryer). In both cases there was no backlog detected. The inspection of the control detergent revealed a moderate residue on all washed samples.

The results of the practical backlog described above Tests were carried out by weighing the on a denim test material deposited residue confirmed. In this test, the Detergent composition according to the invention by a Filtered sample of denim material, washing with tel in solution-suspension in 0.12% concentration in what water of 24 ° C and a hardness of 200 ppm (as CaCO₃) det. The weight of the residue on the fabric is noted and compared. In this test, the backlog was in the ver equal to that of the control sample only about 75% what a significant difference in the appearance of the washed means products.

The above-mentioned adhesion test, which is the stickiness for washing telproducts is that 10 g of the base beads (or the detergent composition in some cases)  placed evenly between two watch glasses that have a diameter of 23 cm, the concave Side of both glasses is facing upwards, and on the top glass weighing 500 g. After 5 minutes After standing for a long time, the weight on the upper glass is removed and the bottom glass turned over, which you see on this watch glass stuck product weighs. The percent detention ability is the number of grams of product on the watch glass remains, multiplied by 10.

The flow index is the value determined in a flow test, at which the volumetric velocity of the base spheres (and in some cases the final product) and standardi compared Ottawa Sand (-209 +60, U.S. sieve range) by measuring the times it takes for a complete Emptying a 1.9 liter Mason tube through a ring Opening with a diameter of 2.2 cm in another Closure attached nozzle measures. The flow index in percent is the time the sand takes divided by the Time that the test product requires, times 100.

Example 2

Hollow spheres like that of Example 1, but with NTA instead part of the carbonate is essentially made in the same manner as in Example 1.  

The wording is only changed by adding 5 parts of the zeolite and 15 parts of the Sodium carbonate in the crutcher through 20 parts of NTA as monohy third of the trisodium salt replaced. The NTA will be launched during the Mixing added after the sodium carbonate. Get the beads are not as strong as those in Example 1 but satisfactorily free flowing. For this product it is sufficient if it contains 12% non-ionic detergent instead of the 19.7% in the product of Example 1, the final percentages of the other components accordingly increase. The product obtained is satisfactory particulate laundry detergent.

According to a modification of this formulation, 2.5 % water-containing sodium silicate added subsequently to achieve anticorrosive properties and magnesium ions bind in the wash water. If the silicate is about the same Has particle size and density, it trickles during transport tes and storage or does not differ from the other components. The product obtained fulfills the A requirement for a conventional heavy-duty detergent, however can put small amounts of zeolite silicate aggregate on the washed materials.

According to another alternative formulation, 3% Sodium silicate with the Na₂O: SiO₂ ratio of about 1: 2.4  incorporated into the end product by adding a aqueous solution thereof, together with 1.5% magnesium sulfate and 0.4% citric acid to gel or to prevent settling in the crutcher. The finished product is a good heavy-duty detergent, but stores more Zeo lith-silicate aggregate on washed, dried on a line materials, as a comparable formulation, in which the water-containing sodium silicate subsequently added had been set.

Example 3

The procedure of Example 2 is with pentasodium tripoly repeated phosphate instead of NTA. The received pro Products are good detergents with a bulk density of around 0.8 g / cm³ (like that of Example 2), but the bulk weights by changing the conditions in the spray skirt voltage tower and the formulations can be varied so that they range from 0.7 to 0.9 g / cm³, and in some In some cases, the bulk weights can be reduced to 0.3 g / cm³ will. If the silicate is subsequently added, the Bulk weights may be slightly higher, especially for that those in the lower part of the area. The product is strong ker free-flowing than that of Example 2, but has about that same washing power.  

In the above formulations and those of the previous ones Examples include an additional portion of bentonite in the crut be given to products containing 15% or to get more bentonite. These products are gone visible their binding effectiveness, the dispersibility and other desirable properties associated with bentonite be written even better and make good wash medium (and base spheres). The tripoly phosphate to be replaced, either in whole or in part, e.g. B. half by tetrasodium pyrophosphate, being similar good products can be obtained.

Example 4

A final detergent product will essentially follow the method of Examples 1 and 2. It contains 30 parts zeolite, 30 parts NTA, 20 parts nonionic wash active substance, 10 parts bentonite, 5 parts sodium carbonate, 5 Parts water and 1.3 parts enzyme. This product has one Bulk density of 0.5 g / cm³ and satisfies a of the detergent. To improve fluidity of the product, however, it is desirable not to contain ionic detergent to ver 15%, preferably 12% wrestle. To increase the bulk density to about 0.7 g / cm³, half of the bentonite can be replaced by sodium silicate (Na₂O:  SiO₂ ratio 1: 2.4) to be replaced, the last compo nente in 47.5% aqueous solution in the crutcher and 1.5 parts of magnesium sulfate and 0.4 parts of lemons Acid can accordingly act as a preventive of gel formation Funds at an earlier time of manufacture of the Crutcher mixture can be added. The product obtained has a bulk density of about 0.7 g / cm³ and can be about 20 parts Absorb non-ionic detergent without being sticky become or have diminishing fluidity. Though camps there are fewer zeolite-silicate agglomerates than formulations, which are conventionally larger quantities of silicate than Crutcher additives contain, but can agglomerate with the Product of washed, line-dried laundry be put.

Example 5

Instead of making hollow spheres on which to form a detergent composition added a detergent a detergent composition can be brought through obtain direct spray drying of a crutcher mixture which a suitable synthetic organic detergent contains. Using essentially the same procedure As in Example 1, a Crutcher mixture is produced which is spray dried. The beads obtained contain 16 parts linear 05896 00070 552 001000280000000200012000285910578500040 0002003206379 00004 05777 tridecylbenzenesulfonate, 20 parts zeolite,  12.5 parts bentonite, 15 parts NTA, 10 parts sodium carbonate and conventional auxiliaries (dye, fluorescent light ler). The bulk weight of the spray-dried product is in the range of 0.3 to 0.8, usually in the lower part this range and is sometimes only 0.2 g / cm³. At the The manufacturing process becomes the organic detergent usually added after the water. Usually becomes dried to a moisture content of about 8 to 12%. The product obtained preferably contains about 3 parts Sodium silicate containing serum, which subsequently is inflicted, along with the other normal auxiliaries substances such as enzymes and perfume. It satisfies of heavy duty laundry detergent that does not contain undesirable amounts Zeolite or zeolite silicate aggregates on the washed Tissue deposits. Because of the presence of the bentonite the detergent appears to disperse very quickly when it is added to wash water and is believed to increase at least partly this rapid dispersion in connection with the presence of bentonite inhibits the storage of zeolite.

Example 6

The procedure of Example 5 is repeated, but the NTA replaced by the same weight of calcined soda. The Product is also a satisfactory full wash with tel.  

Although the silicate, if it should be available, preferably later as water-containing sodium silicate can be added up to add 5 parts of silicate to the crutcher with suitable amounts of magnesium sulfate and citric acid, as described in the preceding examples, whereupon useful detergent compositions, although a certain zeolite-silicate deposit occurs.

Except for the conventional materials that were added later can be set softening to the products of the examples Amounts of a cationic material, e.g. B. 8% dimethyl-di stearyl-ammonium chloride, an amphoteric detergent, e.g. B. 5% Miranol C₂M® (1-carboxymethyl-1-carboxyethoxyethyl- 2-coconut imidazolinium betaine) or a bleach, e.g. B. 15% sodium perborate (preferably activated) are given. Of course, the addition of these materials reduces the proportions of the other components in the final composite composition, thereby reducing the properties of the compositions something to be changed so that sometimes more in the wash water  Product is required to have the same cleaning effect to achieve.

In Examples 5 and 6, the linear tridecylbenzene can fonat by the same weight of sodium lauryl sulfate or Sodium lauryl polyethoxy sulfate (3 to 10 EtO) or mixtures of these materials will be replaced in equal parts. The Products obtained can also be used as detergents. Similarly, instead of the carbonate's NTA, the carbonate and the bicarbonate, the natri umzitrat and / or the sodium gluconate are replaced, at at least partially, e.g. B. a quarter or a half, whereupon good detergents are obtained.  

Example 7

Essentially following the procedure of Example 1 a Crutcher mixture of 36.9 parts water, 1.2 parts Fluorescence brightener (Tinopal 5BM®, extra concentrated) 0.1 Part ultramarine blue, 2.1 parts magnesium sulfate (heptahydrate) 0.3 parts sodium citrate, 22.4 parts zeolite 4A powder (par hydrated to a moisture content of approximately 20%), 20.9 parts of trisodium nitriloacetate monohydrate, 7.4  Share a 47.5% solution of sodium silicate (Na₂O: SiO₂ = 1: 2.4), 3.7 parts of sodium bentonite, 2.8 parts of natural anhydrous soda and 2.1 parts of a mineral compound for elevation the porosity of the hollow spheres and as a builder poses. The crutcher mix was made in the same way spray dried as previously described, taking the loss moisture in the drying stage was about 45.2%.

To 78.4 parts of the spray-dried hollow beads with part size according to a mesh size of 2.00 mm to 0.149 mm (sieved), 20 parts of Neodol 23-6.5® sprayed, whereupon the beads with 1.3 parts proteolytic Enzyme of high activity were mixed and then 0.3 Parts of perfume were sprayed. The end product has a Zeo lith content of 25%, an NTA content of 30%, a sodium bentonite content of 5% and a content of water-soluble Na trium silicate of 5%. The moisture content was 5% and the content of detergent (polyethoxylated higher Fatty alcohol) 20%. The bulk density was about 0.7 g / cm³ and the pH of a 1% solution about 10.

The detergent composition thus prepared is a satisfactory non-ionic heavy-duty detergent but is stored on a washed, dried on a line  Fabric a little more zeolite-silicate aggregate than one ent speaking composition without water-soluble silicate solids was produced. One prefers ent in such speaking compositions that also about 0.1 to 0.5 % Low molecular weight sodium polyacrylate of the previous described type is included. Both products wash laundry good and are particularly effective for cold water washing, at least in part due to the bentonite content and the proximity for instant dispersion, which is observed when that Detergent is added to the washing water (this dispersion also reduces the time for implementation between the soluble silicate and the zeolite forming undesirable aggregates).

Claims (27)

1. Free-flowing, spray-dried hollow spheres which can be used to prepare a particulate detergent composition containing builders and nonionic surfactant, characterized in that they are on a weight basis

• 5 to 60% zeolite exchangeable for calcium ions of 200 to 400 milligram equivalent calcium carbonate hardness per g anhydrous zeolite,
• - 2 to 40% bentonite with at least 2% moisture on an anhydrous bentonite basis,
• 5 to 60% water-soluble builders or a mixture of these builders, namely polyphosphate, pyrophosphate, orthophosphate, borate, nitrilotriacetate, citrate, gluconate, carbonate or bicarbonate, and
• Contain 0 to 30% of water-soluble synthetic organic detergent, where,
• - if water-soluble synthetic detergent is not present, bicarbonate is excluded as a water-soluble builder, and
• - If anionic detergent is present as a water-soluble synthetic detergent, a phosphate salt is excluded as a water-soluble builder.

2. hollow spheres according to claim 1, characterized in that they also contain 0 to 5% water-soluble silicate. 3. hollow spheres according to claim 2, characterized in that they have a bulk density of 0.2 to 0.9 g / cm³ and part sizes from 2.0 mm to 0.149 mm Mesh size, the zeolite 15 to 25 wt .-% hydration water, the bentonite is a swelling clay with a Swellability in water from 3 to 15 ml / g and one Viscosity from 3 to 30 mPa · s at 6% concentration in  Water and the water-soluble silicate are an alkali metal (M) silicate with an M₂O: SiO₂ ratio of 1: 1.6 to 1: 3 is. 4. hollow spheres according to claim 3, characterized in that the ratio bentonite to zelith 1: 4 to 1: 1, the ratio nis water-soluble builders to zeolite 1: 2 to 3: 1 and the ratio of bentonite to water-soluble builders 1:10 is up to 1: 1. 5. hollow spheres according to claim 4, characterized in that they 10 to 40% hydrated sodium zeolite, 2 to 35% Bentonite with a swelling capacity of 7 to 15 ml / g and one Viscosity from 8 to 30 mPa · s at 6% concentration in Water, 10 to 50% water-soluble alkali metal builder salt, 0 to 25% water-soluble synthetic anionic organic Active detergents and 0 to 3% water-soluble silicate contain. 6. hollow spheres according to claim 5, characterized in that they 15 to 35% Zeolite A, 5 to 20% processed Wyoming Bentonite, 20 to 50% water-soluble sodium builder salt, 0 up to 20% water-soluble synthetic anionic orga African detergent and 0% sodium silicate contain that Ratio of bentonite to zeolite 1: 3 to 2: 3, the ratio water-soluble builders to zeolite 2: 3 to 2: 1 and that Ratio of bentonite to water-soluble builders 1: 6 to Is 1: 2. 7. hollow spheres according to claim 2, characterized in that the water-soluble builders made of carbonate, bicarbonate, Polyphosphate, nitrilotriacetate or a mixture of these There are builders and the bentonite is anhydrous Bentonite base contains at least 3% moisture.   8. hollow spheres according to claim 7, characterized in that the bentonite contains at least 4% moisture, the water soluble builder comprises a nitrilotriacetate and no water-soluble synthetic organic wash active substance and no water-soluble silicate is present. 9. hollow spheres according to claim 8, characterized in that 15 to 40% hydrated zeolite A with 15 to 25% by weight Water of hydration, 10 to 20% treated Wyoming Bentonite with a swelling capacity of 7 to 15 ml / g and one Viscosity from 3 to 30 mPa · s at 6% concentration in Water and 20 to 60% trisodium nitrilotriacetate (NTA) contain. 10. hollow spheres according to claim 7, characterized in that the bentonite contains at least 4% moisture, the water soluble builder comprises a polyphosphate and none water soluble synthetic organic detergent and there is no water-soluble silicate. 11. hollow spheres according to claim 10, characterized in that they 20 to 40% hydrated zeolite A with 15 to 25% by weight Water of hydration, 10 to 20% treated Wyoming Bentonite with a swelling capacity of 7 to 15 ml / g and one Viscosity from 3 to 30 mPa · s at 6% concentration in Contain water and 20 to 60% sodium tripolyphosphate. 12. hollow spheres according to claim 2, characterized in that they are 5 to 30% water-soluble synthetic organic Contain detergent. 13. Hollow beads according to claim 12, characterized in that the water-soluble synthetic organic detergent is an anionic detergent.   14. Hollow beads according to claim 13, characterized in that the anionic detergent from linear sodium alkylbene benzenesulfonate containing 10 to 18 carbon atoms Alkyl group, the sodium salt of a fatty alcohol sulfate, in which the alcohol contains 10 to 18 carbon atoms, or which Sodium salt of a fatty alcohol ethoxylate sulfate, the Fatty alcohol has 10 to 18 carbon atoms and the 3 to Contains 30 ethylene oxide groups per mole, or from a mixture of 2 or more of these detersives, and the proportion of anionic detergent substances in the hollow spheres 5 to Is 25%. 15. hollow spheres according to claim 7, characterized in that they are 3 to 30% water soluble synthetic anionic contain organic detergent. 16. hollow spheres according to claim 15, characterized in that the anionic detergent from a linear Sodium alkylbenzenesulfonate with a 10 to 18 carbon atom-containing alkyl group, the sodium salt of a Fatty alcohol sulfate in which the alcohol has 10 to 18 carbon contains atoms, or the sodium salt of a fat alcohol ethoxylate sulfate, the fatty alcohol 10 to Has 18 carbon atoms and 3 to 30 ethylene oxide contains groups per mole, or a mixture of 2 or several of these detergents, and the proportion of anionic washing agents in the hollow spheres 5 to 25% is. 17. Hollow beads according to claim 7, characterized in that they do not have a water-soluble synthetic organic Active detergent and no water-soluble silicate. 18. Hollow spheres according to claim 2, characterized in that they 0.5 to 1% polyacrylate with a molecular weight of 1000 to 5000 included.   19. Hollow beads according to claim 3, characterized in that they have a bulk density of 0.2 to 0.8 g / cm³, the Zeolite consists of hydrated zeolite A, the bentonite at least 3% moisture based on anhydrous Contains bentonite, the water-soluble builder from one Sodium salt of nitrilotriacetic acid is what Water-soluble silicate, if present, sodium silicate with a Na₂O: SiO₂ ratio of 1: 2 to 1: 2.8 is the Moisture content of the beads is 3 to 12%, that Bentonite: zeolite ratio 1: 6 to 1: 2, the ratio NTA: zeolite 1: 2 to 2: 1 and the ratio bentonite: NTA 1: 6 is up to 1: 2 and the percentages of hydrated Zeolite, bentonite, sodium nitrilotriacetate or silicate 10 up to 40%; 2 to 25%; Make up 10 to 40% or 0 to 5%. 20. Hollow beads according to claim 3, characterized in that they have a bulk density of 0.2 to 0.8 g / cm³, 5 to 30% a synthetic anionic organic detergent containing and the zeolite is hydrated zeolite A which Bentonite based on anhydrous bentonite at least 3% Contains moisture, the water-soluble builders a sodium salt of nitrilotriacetic acid, which synthetic anionic organic detergent linear Sodium alkyl benzene sulfonate having 10 to 19 carbon atoms containing alkyl groups, the sodium salt of a fatty alcohol sulfate in which the alcohol has 10 to 18 carbon atoms contains or the sodium salt of a fatty alcohol ethoxylate is sulfate containing 3 to 30 ethylene oxide groups per mole and in which the fatty alcohol has 10 to 18 carbon atoms has, or from a mixture of two or more of these detergent active ingredients, the water-soluble silicate, if available, sodium silicate with a Na₂O: SiO₂- Ratio of 1: 2 to 1: 2.8, the moisture content of the Hollow beads is 3 to 12%, the ratio Bento nit: zeolite 1: 6 to 1: 1, the ratio NTA: zeolite 1: 3 to 3: 1, the ratio bentonite: NTA 1:10 to 1: 1 and that  Ratio of synthetic anionic organic detergent fabric: zeolite is 1: 1 to 1: 4 and the percentages hydrated zeolite, bentonite, sodium nitrilotriacetate, synthetic anionic organic detergent or Silicate 10 to 40%; 2 to 25%; 10 to 40; 10 to 25 or Make up 0 to 5%. 21. Hollow spheres according to claim 3, characterized in that they have a bulk density of 0.2 to 0.8 g / cm³, the Zeolite consists of hydrated zeolite A, the bentonite on water-free bentonite basis at least 3% moisture contains the water-soluble builders from pen sodium tripolyphosphate or tetrasodium pyrophosphate or a mixture of the two, the water-soluble Silicate, if present, sodium silicate with a Na₂O: SiO₂ ratio of 1: 2 to 1: 2.8 is the moisture is from 3 to 12%, the Bentonite: zeolite ratio 1: 6 to 1: 2, the ratio Total polyphosphate to zeolite 1: 2 to 2: 1 and the ratio Bentonite to total polyphosphate 1: 6 to 1: 2 and that Percentages of hydrated zeolite, bentonite, total poly phosphate or silicate 15 to 35%; 5 to 20%; 15 to 40% or 0 to 5%. 22. Use of the hollow spheres according to claim 1 for manufacturing a detergent composition by absorbing one nonionic detergent on the hollow spheres in an amount of 8 to 30% of the detergent composition. 23. Use of the hollow spheres according to claim 2 for the production a detergent composition by absorbing one nonionic detergent in an amount of 8 to 30% the detergent composition. 24. Use according to claim 23, characterized in that the non-ionic detergent from a condensation product  from 6 to 12 moles of ethylene oxide and a higher fatty alcohol with 12 to 16 carbon atoms and the proportion of nonionic detergent active in composition 10 is up to 25%. 25. Use of the hollow spheres according to claim 17 for the production a detergent composition by absorbing one nonionic detergent active on the hollow spheres in one Amount from 8 to 30% of the detergent composition. 26. Use according to claim 25, characterized in that the non-ionic detergent from a condensation product from 6 to 22 moles of ethylene oxide and a higher fatty alcohol with 12 to 16 carbon atoms, and the proportion of nonionic detergent 10 to 25% of the total setting is. 27. Use of the hollow spheres according to claim 17 and the Hollow spheres according to claim 25 for the production of a Detergent composition, characterized in that this present in a weight ratio of 1:10 to 10: 1, their particles sizes in the range of 2.00 mm to 0.419 mm mesh size lie, the bulk density of the hollow spheres before Ver mix the two in a range within 0.1 g / cm³ and the bulk density of the final composition was 0.2 is up to 0.9 g / cm³.